JPH07247357A - Polyimide resin having excellent fatigue properties, the composition and injection molded article - Google Patents

Abstract

(57) [Summary] [Structure] Formula (I), Formula (II) and Formula (III) With an amine compound and a tetracarboxylic acid dianhydride component, a dicarboxylic acid anhydride, or a melt-moldable polyimide resin excellent in fatigue properties obtained by reacting in the presence of a monoamino compound, and a polyimide Resin composition and injection-molded body thereof. [Effects] According to the method of the present invention, a polyimide resin composition and an injection-molded article having excellent fatigue resistance are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin having good fatigue properties. More specifically, the present invention relates to a polyimide resin having good melt moldability and excellent fatigue resistance, a polyimide resin composition containing the polyimide resin and a fibrous reinforcing material, and injection molded articles thereof.

[0002]

2. Description of the Related Art Conventionally, in addition to its high heat resistance, polyimide has excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. Widely used in such fields. Conventionally, various polyimides that have excellent properties have been developed, but even if they have excellent heat resistance, they do not have a clear glass transition temperature, so when they are used as molding materials, they are processed using methods such as sintering molding. It has to be processed or has excellent workability, but has a low glass transition temperature, and is soluble in halogenated hydrocarbon solvents, which is not satisfactory in terms of heat resistance and solvent resistance. There were advantages and disadvantages. For the purpose of solving these problems, the present inventors previously developed melt-moldable polyimides and various copolyimides having excellent mechanical properties, thermal properties, electrical properties, and chemical resistance ( Kaisho 61
-143478, 62-205124, and Japanese Patent Application No. 63-270778). However, studies on dynamic mechanical properties such as fatigue properties have not been carried out so much, and it is the current situation that there is little knowledge especially in the field of highly heat-resistant polyimide capable of injection molding which has been recently developed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a polyimide resin composition which can be melt-molded such as injection molding and has high fatigue properties, and an injection-molded article thereof. Generally, the fatigue properties of resins are entangled at the molecular level,
That is, it is said that as the crosslink density increases, it improves. However, in the case of a high heat resistant resin as an injection molding material used in the present application, there is a problem that if the molecular weight is increased for the purpose of increasing the entanglement of molecules, the injection moldability is significantly impaired.

[0004]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have earnestly sought a method for improving fatigue properties by increasing only the entangled state at the molecular level without extremely increasing the molecular weight. As a result of examination, the polyimide resin obtained by the specific method has excellent melt flow moldability,
Moreover, they have found that an injection-molded article excellent in fatigue properties can be obtained from this resin and a polyimide resin composition composed of this resin group and carbon fiber, and reached the present invention. That is, the present invention has the formula (I)

[0005]

[Chemical 5] means. ) With respect to 1 mol of the diamine compound represented by the following formula (II)

[0006]

[Chemical 6] And a tetraamino compound represented by the following formula (III)

[0007]

[Chemical 7] Means ), The sum of the triamino compounds represented by
An amine compound of 005 to 0.11 mol and the following formula (I
V) [Chemical 8]

[0008]

[Chemical 8] Means ), Which is obtained by reacting a tetracarboxylic acid dianhydride component with a dicarboxylic acid anhydride or a monoamino compound in the presence or absence of the compound, and is capable of being melt-molded with excellent fatigue properties. Another polyimide resin, a polyimide resin composition comprising the polyimide resin and a fibrous reinforcing material, and an injection molded article thereof. Specifically, with respect to 1 mol of the tetracarboxylic dianhydride represented by the above formula (IV), the diamine compound represented by the above formula (I) and the tetraamino compound represented by the above formula (II) And / or the sum of amino compounds having two or more amino groups consisting of the triamino compound represented by the above formula (III) is 0.8 to 1.20 mol, which is excellent in fatigue properties. A melt-moldable polyimide resin, and a polyimide resin composition comprising the polyimide resin and a fibrous reinforcing material, and an injection molded article thereof,
More specifically, 0.001 to 0..25 per 1 mol of the total amount of the tetracarboxylic dianhydride represented by the above formula (IV).
Melt-moldable polyimide resin excellent in fatigue characteristics, characterized by using 20 mol of dicarboxylic acid anhydride and / or monoamine, polyimide resin composition comprising the polyimide resin and fibrous reinforcing material, and injection molded article thereof Is.

When synthesizing a melt-moldable polyimide resin having excellent fatigue properties in the present invention, an amino compound having two or more amino groups is used as a raw material monomer. As the amino compound, a diamine compound represented by the above formula (I), a tetraamino compound represented by the above formula (II) and / or a triamino compound represented by the above formula (III) is used. It is essential that the total amount of the tetraamino compound and / or the triamino compound be used in an amount of 0.005 to 0.11 mol ratio with respect to 1 mol of the diamine compound.

The diamine compound used in the present invention is represented by the above formula (I), that is, 4,4'-bis (3-aminophenoxy) biphenyl and bis [4- (3-aminophenoxy). Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] -1,1,1,
Although it is 3,3,3-hexafluoropropane, there is no problem even if these diamine compounds are used alone or in combination of two or more. Further, other diamines may be mixed and used as long as the properties of the polyimide are not impaired. Examples of the diamine that can be mixed and used include, for example,
m-phenylenediamine, o-phenylenediamine, p
-Phenylenediamine, m-aminobenzylamine, o
-Aminobenzylamine, 3-chloro-1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2, 6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-methoxy-1,4-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-
Methoxy-1,3-phenylenediamine, benzidine,
3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,

4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane,
1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) Phenyl] propane, 1,2-bis [4
-(4-aminophenoxy) phenyl] propane, 1,
3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4-
(4-Aminophenoxy) phenyl] butane, 1,4-
Bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3- Methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,
5-dimethylphenyl] propane, 2,2-bis [4-
(4-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1 , 3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy)
Benzene, 1,3-bis (3-aminophenoxy) benzene 1,4-bis (4-aminophenoxy) benzene,
4,4'-bis (4-aminophenoxy) biphenyl,
Bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-amino) Phenoxy) phenyl] sulfone,

Bis [4- (3-aminophenoxy) phenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1, 3-bis [4-
(3-Aminophenoxy) benzoyl] benzene, 1,
4-bis [4- (3-aminophenoxy) benzoyl]
Benzene, 4,4'-bis (3-aminophenoxy) benzoyl] benzene, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-
Bis (3-aminophenoxy) -3,3 ', 5,5'-
Tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3 ′, 5,5′-tetrabromobiphenyl, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-amino Phenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, and the like.

The tetraamino compound and / or triamino compound used in the present invention is represented by the above formula (II) and / or formula (III), and is 3,3'-
Diaminobenzidine, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenyl sulfone, 3,3 ′ , 4,4'-Tetraaminodiphenyl sulfide, 1,2,4-triaminobenzene, 2,4,6-triaminopyrimidine, 3,
3 ', 4, -triaminobenzophenone, 3,3',
4, -triaminobiphenyl, 3,3 ', 4, -triaminodiphenyl ether, 3,3', 4, -triaminodiphenyl sulfone, 3,3 ', 4, -triaminodiphenyl sulfide, 3,4,4 '-Triaminobenzophenone, 3,4,4'-triaminobiphenyl, 3,
4,4'-triaminodiphenyl ether, 3,4
4'-triaminodiphenyl sulfone, 3,4,4'-
Triaminodiphenyl sulfide, 1,3,5-tris (3-aminophenoxy) benzene, 1,3,5-tris (4-aminophenoxy) benzene, 1,3,5-tris (2-aminophenoxy) benzene However, basically, it only has to form an entanglement point (crosslinking point) in the molecular chain, and 2,3′-diaminobenzidine, 2,2′-diaminobenzidine, 3,3 ′, 2,2 ′ -Triaminobiphenyl, 3,4 ', 2,2'-tetraaminobiphenyl, 3,3', 2,4'-tetraaminobiphenyl,
2,2 ', 4,4'-tetraaminobenphenone, 2,
3 ', 4,4'-tetraaminobenphenone, 2,
2 ', 3,3'-tetraaminobenphenone, 2,
2 ', 3,4'-tetraaminobenphenone, 3,
3 ', 2,4'-tetraaminobenphenone, 2,
2 ', 4,4'-tetraaminodiphenyl ether,
2,3 ', 4,4'-tetraaminodiphenyl ether, 2,2', 3,3'-tetraaminodiphenyl ether, 2,2 ', 3,4'-tetraaminodiphenyl ether, 3,3', 2,4 '-Tetraaminodiphenyl ether, 2,2', 4,4'-tetraaminodiphenyl sulfone, 2,3 ', 4,4'-tetraaminodiphenyl sulfone, 2,2', 3,3'-tetra Aminodiphenyl sulfone, 2,2 ', 3,4'-tetraaminodiphenyl sulfone, 3,3', 2,4'-tetraaminodiphenyl sulfone, 2,2 ', 4,4'-tetraaminodiphenyl sulfide, 2 , 3 ', 4,4'-tetraaminodiphenyl sulfide, 2,2', 3,3'-tetraaminodiphenyl sulfide, 2,2 ', 3,4'
-Tetraaminodiphenyl sulfide, 3,3 ', 2
4'-tetraaminodiphenyl sulfide,

1,2,4,5-tetraaminobenzene,
1,2,3,4-tetraaminobenzene, 1,2,3
5-tetraaminobenzene, 1,3,4,5-tetraaminobenzene, 2,3,4,5-tetraaminobiphenyl, 2,4,5,6-tetraaminobiphenyl, 2,
3,5,6-tetraaminobiphenyl, 2,3,4,5
-Tetraaminobenzophenone, 2,4,5,6-tetraaminobenzophenone, 2,3,5,6-tetraaminobenzophenone, 2,3,4,5-tetraaminodiphenyl sulfone, 2,4,5,6- Tetraaminodiphenyl sulfone, 2,3,5,6-tetraaminodiphenyl sulfone, 2,3,4,5-tetraaminodiphenyl ether, 2,4,5,6-tetraaminodiphenyl ether, 2,3,5,6- Tetraaminodiphenyl ether, 2,3,4,5-tetraaminodiphenyl sulfide, 2,4,5,6-tetraaminodiphenyl sulfide, 2,3,5,6-tetraaminodiphenyl sulfide, 1,2,4-tri Aminobenzene, 1,2,3-
Triaminobenzene, 1,3,5-triaminobenzene, 2,4,6-triaminopyridine, 2,3,4-triaminopyridine, 3,4,5-triaminopyridine,
2,3,5-triaminopyridine, triamterene,
3,4 ′, 4, -triaminobenzophenone, 3,
2 ', 4-triaminobenzophenone, 3,2', 2-
Triaminobenzophenone, 3,3 ', 2-triaminobenzophenone, 3,4', 2-triaminobenzophenone, 2,3 ', 4-triaminobenzophenone, 2,
2 ', 4-triaminobenzophenone, 2,4', 4-
Triaminobenzophenone,

3,4 ', 4, -triaminobiphenyl,
3,2 ', 4, -triaminobiphenyl, 3,2',
2, -triaminobiphenyl, 3,3 ', 2, -triaminobiphenyl, 3,4', 2, -triaminobiphenyl, 2,3 ', 4, -triaminobiphenyl, 2,
2 ', 4, -triaminobiphenyl, 2,4', 4,-
Triaminobiphenyl, 3,4 ', 4, -triaminodiphenyl ether, 3,2', 4, -triaminodiphenyl ether, 3,2 ', 2, -triaminodiphenyl ether, 3,3', 2, -triamino Diphenyl ether, 3,4 ′, 2, -triaminodiphenyl ether, 2,3 ′, 4, -triaminodiphenyl ether,
2,2 ', 4, -triaminodiphenyl ether, 2,
4 ', 4, -triaminodiphenyl ether, 3,
4 ', 4, -triaminodiphenyl sulfone, 3,
2 ', 4, -triaminodiphenyl sulfone, 3,
2 ', 2, -triaminodiphenyl sulfone, 3,
3 ', 2, -triaminodiphenyl sulfone, 3,
4 ', 2, -triaminodiphenyl sulfone, 2,
3 ', 4, -triaminodiphenyl sulfone, 2,
2 ', 4, -triaminodiphenyl sulfone, 2,
4 ', 4, -triaminodiphenyl sulfone, 3,
4 ', 4, -triaminodiphenyl sulfide, 3,
2 ', 4, -triaminodiphenyl sulfide, 3,
2 ', 2, -triaminodiphenyl sulfide, 3,
3 ', 2, -triaminodiphenyl sulfide, 3,
4 ', 2, -triaminodiphenyl sulfide, 2,
3 ', 4, -triaminodiphenyl sulfide, 2,
2 ', 4, -triaminodiphenyl sulfide, 2,
4 ', 4, -triaminodiphenyl sulfide, 2,
3,4-triaminobenzophenone, 2,3,5-triaminobenzophenone, 2,4,5-triaminobenzophenone, 2,3,4-triaminobiphenyl, 2,
3,5-triaminobiphenyl, 2,4,5-triaminobiphenyl, 2,3,4-triaminodiphenyl ether, 2,3,5-triaminodiphenyl ether,
2,4,5-triaminodiphenyl ether,

2,3,4-triaminodiphenyl sulfone, 2,3,5-triaminodiphenyl sulfone, 2,
4,5-triaminodiphenyl sulfone, 2,3,4-
Triaminodiphenyl sulfide, 2,3,5-triaminodiphenyl sulfide, 2,4,5-triaminodiphenyl sulfide, 1,3-bis (3-aminophenoxy) -5- (2-aminophenoxy) benzene, 1 ，
3-bis (3-aminophenoxy) -5- (4-aminophenoxy) benzene, 1,3-bis (2-aminophenoxy) -5- (3-aminophenoxy) benzene,
1,3-bis (2-aminophenoxy) -5- (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) -5- (3-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) -5- (2
-Aminophenoxy) benzene, 1- (3-aminophenoxy) -3- (4-aminophenoxy) -5- (2-
Any tetraamino compound and / or triamino compound such as aminophenoxy) benzene can be used.

These tetraamino compounds and / or triamino compounds may be used alone or in combination of two or more as long as the total amount thereof is in the range of 0.005 to 0.11 with respect to 1 mol of the diamine compound. . When the total amount of these tetraamino compounds and / or triamino compounds is 0.005 mol or less with respect to 1 mol of the diamine compound, entanglement of molecules cannot be sufficiently formed and improvement of fatigue properties cannot be expected. On the other hand, when the amount is 0.11 mol or more, the number of entanglement points (crosslinking points) of the molecules becomes too large and the melt fluidity is significantly hindered. The amount of the tetraamino compound and / or triamino compound used is preferably 0.01 to 0.06 mol, and particularly preferably 0.02 to 0.04 mol, relative to 1 mol of the diamine compound.

When synthesizing the polyimide of the present invention,
As the tetracarboxylic dianhydride component, a tetracarboxylic dianhydride represented by the formula (IV), that is, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride is used, but there is no problem even if these are used alone or in combination of two or more.

Further, other tetracarboxylic acid dianhydrides may be mixed and used as long as the characteristics of the polyimide are not impaired. Examples of tetracarboxylic dianhydrides that can be mixed and used include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Benzophenone tetracarboxylic dianhydride, 2,2 ', 3
3'-benzophenone tetracarboxylic acid dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl)- 1,1,1,3,3,3-trifluoromethylpropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, Bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3
-Dicarboxyphenyl) methane dianhydride, bis (3,3
4-dicarboxyphenyl) methane dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride Anhydrous, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3 -Dicarboxyphenoxy)
Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6
-Naphthalenetetracarboxylic dianhydride, 1,2,3,
4-benzenetetracarboxylic dianhydride, 3, 4, 9,
10-perylene tetracarboxylic dianhydride, 2,3
6,7-anthracene tetracarboxylic dianhydride, 1,
2,7,8-phenanthrenetetracarboxylic acid dianhydride and the like can be mentioned.

In the production of the polyimide resin of the present invention, dicarboxylic acid anhydride or monoamine is used for the purpose of sealing the polymer molecular ends. Specific examples of these compounds include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4- Dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride Substance, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,8-
Examples thereof include naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride. These dicarboxylic acid anhydrides may be substituted with a group having no reactivity with amines or dicarboxylic acid anhydrides. These may be used alone or in combination of two or more. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used.

Examples of monoamines include the following. For example, aniline, o-toluidine, m
-Toluidine, p-toluidine, 2,3-xylidine,
2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline,
p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline,
p-nitroaniline, m-nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o -Aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenznitrile, p-aminobenznitrile, m-aminobenznitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-amino Phenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-
Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4
-Aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-
Naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino-1-nafrole, 5-
Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. Usually, of these aromatic monoamines, derivatives of aniline are preferably used. These may be used alone or in combination of two or more. These aromatic monoamines and / or dicarboxylic acid anhydrides may be used alone or
There is no problem even if two or more species are mixed and used. The amount of these compounds used is 1 to 3 times mol of the monoamine (the difference between the total number of amino groups of the amine compound having two or more amino groups and the number of acid anhydride groups of tetracarboxylic dianhydride). The excess component may be tetracarboxylic dianhydride) or dicarboxylic acid anhydride (the excess component is an amine compound), but it is generally used in an amount of about 0.01 mol times that of at least one component. The amount of the compound used as the polymer end-capping agent is the difference between the total number of amino groups of the amine compound having two or more amino groups and the number of acid anhydride groups of the tetracarboxylic dianhydride. 1-2
It is preferable that it is a double mole of monoamine (excess component is tetracarboxylic acid dianhydride) or dicarboxylic acid anhydride (excess component is amine compound), but more preferably 1 to
It is 1.5 times the molar amount.

The method for producing the polyimide resin in the present invention can be produced by any known method. That is, 1) Polyamic acid is isolated by synthesizing polyamic acid in an organic solvent and removing the solvent at a low temperature by using a method such as vacuum distillation or discharging the obtained polyamic acid solution into a poor solvent. Then, this is heated to imidize to obtain a polyimide. 2) After preparing the polyamic acid solution in the same manner as 1),
A method in which a dehydrating agent typified by acetic anhydride is added, and a catalyst is added if necessary to chemically imidize the polyimide, and then the polyimide is isolated by a known method, and washed and dried if necessary. 3) A method in which a polyamic acid solution is obtained in the same manner as in 1), and then the solvent is removed by reduced pressure or heat treatment, and at the same time, thermal imidization is performed. 4) A method in which raw materials are charged into an organic solvent and then heated to simultaneously perform the synthesis of polyamic acid and the imidization reaction, and to make a catalyst, an azeotropic agent, and a dehydrating agent coexist if necessary. And so on.

In the production, it is particularly preferable to carry out the reaction in an organic solvent, and examples of the organic solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N
-Dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
N-methylcaprolactam, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide,
Phenol, o-cresol, m-cresol, p-cresol, cresylic acid, o-chlorophenol, m-
Examples include chlorophenol, p-chlorophenol, anisole and the like. Also, these organic solvents alone,
Also, two or more kinds may be mixed and used.

In the method of the present invention, a method for adding and reacting an amine compound having two or more amino groups, a tetracarboxylic dianhydride, and a dicarboxylic acid anhydride or an aromatic monoamine in an organic solvent is as follows: (A) A method in which a tetracarboxylic acid dianhydride is reacted with an amine compound having two or more amino groups and then a dicarboxylic acid anhydride or an aromatic monoamine is added to continue the reaction. (B) A dicarboxylic acid anhydride is added to an amine compound having two or more amino groups and reacted, and then tetracarboxylic dianhydride is added to continue the reaction, or an aromatic monoamine is added to the tetracarboxylic acid dianhydride. A method of continuing the reaction by adding the amine compound and then adding the amine compound. (C) A method in which a tetracarboxylic dianhydride, an amine compound having two or more amino groups, and a dicarboxylic acid anhydride or an aromatic monoamine are simultaneously added to react. There is no problem even if either method is used.

As a method of adding the amine compound, even if the diamine compound and the tetraamino compound and / or the triamino compound are added separately, the diamine compound and the tetraamino compound and / or the triamino compound are mixed in advance and then added simultaneously. Then there is no problem. The reaction temperature is usually 300 ° C. or lower, and the reaction pressure is not particularly limited and can be sufficiently carried out at normal pressure. The reaction time is
Although it depends on the type of amine compound, the type of tetracarboxylic dianhydride, the type of solvent, the presence or absence of a catalyst, and the reaction temperature, 4 to 24 hours is usually sufficient. The polyimide resin of the present invention is obtained by the above method.

The polyimide resin composition of the present invention is a reinforcing material for the above-mentioned polyimide resin, such as carbon fiber,
It is adjusted by adding a fibrous reinforcing material such as glass fiber, aromatic polyamide fiber and potassium titanate fiber. The amount of the reinforcing material added is 5 to 100 parts by weight, preferably 10 to 5 parts by weight, based on 100 parts by weight of the polyimide resin.
0 parts by weight.

Carbon fiber is most preferred as the type of reinforcing material. As a method for adding the reinforcing material, a generally known method is used, but the polyimide powder and the reinforcing material are premixed by using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender, and then melted. The most common method is to obtain a pellet or powder mixture using a mixer, a hot roll, or the like.

Further, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, etc. may be used as long as the object of the present invention is not impaired.
It is also possible to blend polysulfone, polyetherimide, polyethersulfone, polyetheretherketone, polyetherketone, polyphenylene sulfide, polyamideimide, modified polyphenylene oxide, other polyimides and thermosetting resins in appropriate amounts.

The polyimide resin composition of the present invention is molded and put into practical use by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method and a rotational molding method. The injection molding method is most preferable from the viewpoint of work efficiency because it has excellent melt fluidity. The injection-molded product obtained from the polyimide resin composition of the present invention can be molded into any shape by changing the shape of the mold, but especially around automobile parts that require excellent dynamic fatigue properties. Is expected to be applied to valve lifters and impellers.

[0030]

The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples. In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: 0.50 g of polyimide powder p
-A mixed solvent of chlorophenol and phenol (90: 1
(0 weight ratio) After heating and dissolving in 100 ml, cooled to 35 ° C. and measured. Glass transition temperature (Tg): measured by DSC (Shimadzu DT-40 series, DSC-41M) at a heating rate of 16 ° C / min. 5% weight loss temperature: DTA-TG (Shimadzu DT-4
0 series, 40M) in air at 10 ° C / mi
Measured at a heating rate of n. Melt viscosity: Measured under a load of 100 Kg using a Shimadzu high-performance flow tester CFT-500.

Synthesis Example 1 4,6'-bis (3-aminophenoxy) biphenyl 3.606 kg (9.8 mol), 3 in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube. ，
21.4 g (0.1 mol) of 3'-diaminobenzidine,
Pyromellitic dianhydride 2.05 kg (9.40 mol), phthalic anhydride 177.6 g (1.2 mol), γ-
138 g (1.5 mol) of picoline and 21.8 Kg of m-cresol were charged, and the mixture was heated to 145 ° C. with stirring under a nitrogen atmosphere. During this period, distillation of about 340 g of water was confirmed. Furthermore, at 140-150 ℃ 4
A time reaction was performed. Then, cool to room temperature,
After discharging into kg of toluene, it was filtered off. The polyimide powder was further washed with toluene, pre-dried at 50 ° C. for 24 hours in a nitrogen atmosphere, and then dried at 240 ° C. for 6 hours to obtain 5.33 kg (yield 97%) of polyimide powder. The logarithmic viscosity of this polyimide is 0.44 dl /
g and Tg were 248 ° C. and the 5% weight loss temperature was 560 ° C. The melt viscosity of the obtained polyimide at 420 ° C. was 5600 poise.

Synthesis Example 2 3,606 kg (9.8 mol) of 4,4'-bis (3-aminophenoxy) biphenyl of Synthesis Example 1, 21.4 g (0.1 mol) of 3,3'-diaminobenzidine, 2.05 kg (9.40 mol) of pyromellitic dianhydride, 177.6 g (1.2 mol) of phthalic anhydride, and 3.496 kg of 4,4′-bis (3-aminophenoxy) biphenyl.
(9.5 mol), 3,3'-diaminobenzidine 53.
5 g (0.25 mol), pyromellitic dianhydride 2.0
4 kg (9.35 mol), phthalic anhydride 192.4 g
5.26 kg (yield 97%) of polyimide powder was obtained in exactly the same manner except that the amount was changed to (1.3 mol). The logarithmic viscosity of this polyimide is 0.50 dl / g, Tg is 250 ° C., 5
The% weight loss temperature was 560 ° C. The melt viscosity of the obtained polyimide at 420 ° C. was 9000 poise.

Synthesis Examples 3 to 7 Polyimide powders were obtained in exactly the same manner except that 4,4'-bis (3-aminophenoxy) biphenyl in Synthesis Example 2 was changed to the diamine compound shown in Table 1. The basic physical properties are collectively shown in Table 1 together with the results of Synthesis Example 2.

Synthesis Examples 8 to 9 Polyimide powders were obtained in exactly the same manner as in Example 2 except that the pyrocarboxylic acid dianhydride of Synthesis Example 2 was changed to the tetracarboxylic acid dianhydride shown in Table 1. The basic physical properties are summarized in Table 1 together with the results of Synthesis Example 2.

[0035]

[Table 1] Table 1 ────────────────────────────────── Synthesis example Diamine tetra polyimide Basic physical properties Compound carboxylic acid η Tg [℃] Td5 [℃] dianhydride [dl / g] ────────────────────────────────── ─ 2 BP * 1) PMDA * 7) 0.50 250 560 3 SO2 * 2) PMDA 0.50 250 550 4 CO * 3) PMDA 0.51 230 545 5 S * 4) PMDA 0.49 210 540 6 BAP * 5) PMDA 0.52 218 535 7 6FBAP * 6) PMDA 0.53 231 528 8 BP BPDA * 8) 0.50 230 565 9 BP BisADA * 9) 0.51 190 520 ───────────────────────── ────────── * 1) 4,4'-Bis (3-aminophenoxy) biphenyl * 2) Bis [4- (3-aminophenoxy) phenyl] sulfone * 3) Bis [4- ( 3-Aminophenoxy) phenyl] ketone * 4) Bis [4- (3-aminophenoxy) phenyl] sulfide * 5) , 2-bis [4- (3-aminophenoxy) phenyl] propane * 6) 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane * 7) Pyromellitic dianhydride * 8) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride * 9) 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride object

Synthesis Example 10 4,4'-bis (3-aminophenoxy) biphenyl 3.643 kg (9.9 mol) was added to a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube. ，
3,5-tris (4-aminophenoxy) benzene 5
9.9 g (0.15 mol), pyromellitic dianhydride 2.05 Kg (9.40 mol), phthalic anhydride 177.
6 g (1.2 mol), 138 g (1.5 mol) of γ-picoline and 21.8 kg of m-cresol were charged, and the mixture was heated to 145 ° C. with stirring under a nitrogen atmosphere. During this period, distillation of about 340 g of water was confirmed. Furthermore, the reaction was carried out at 140 to 150 ° C. for 4 hours. Then, the mixture was cooled to room temperature, discharged into 80 kg of toluene, and then filtered. The polyimide powder was further washed with toluene, pre-dried at 50 ° C. for 24 hours in a nitrogen atmosphere, and then dried at 240 ° C. for 6 hours to obtain 5.33 kg (yield 97%) of polyimide powder. This polyimide had an inherent viscosity of 0.49 dl / g, a Tg of 248 ° C. and a 5% weight loss temperature of 560 ° C. 4 of the obtained polyimide
The melt viscosity at 20 ° C. was 5800 poise.

Synthesis Examples 11 to 14 Synthesis Example 10 was changed by changing the molar ratio of 4,4'-bis (3-aminophenoxy) biphenyl and 1,3,5-tris (4-aminophenoxy) benzene in Synthesis Example 10. A polyimide powder having a logarithmic viscosity of about 0.50 dl / g was synthesized according to the method of 1. The molar ratio of 4,4′-bis (3-aminophenoxy) biphenyl and 1,3,5-tris (4-aminophenoxy) benzene and 42 of the obtained polyimide.
The relationship between the melt viscosities at 0 ° C. is summarized in Table 2 together with the results of Synthesis Example 10.

Synthetic Examples 15 to 17 59.9 g (0.15 mol) of 1,3,5-tris (4-aminophenoxy) benzene in Synthetic Example 10 is shown in Table 2.
A polyimide powder was obtained in exactly the same manner except that the triamino compound (0.15 mol) shown in was changed. Table 2 shows the relationship between the molar ratio of 4,4′-bis (3-aminophenoxy) biphenyl and the triamino compound and the melt viscosity of the obtained polyimide at 420 ° C. together with the result of Synthesis Example 10.

Synthesis Examples 18 to 19 In accordance with the method of Synthesis Example 2 by changing the molar ratio of 4,4'-bis (3-aminophenoxy) biphenyl and 3,3'-diaminobenzidine in Synthesis Example 2, the logarithmic viscosity of 0. 5
A polyimide powder of about 0 dl / g was synthesized. 4,4'-
Bis (3-aminophenoxy) biphenyl and 3,3'-
The molar ratio of diaminobenzidine and 4 of the obtained polyimide
The relationship between the melt viscosities at 20 ° C. is shown together with the results of Synthesis Example 2 in Table 2.

Synthesis Example 20 3,3'-diaminobenzidine in Synthesis Example 2 was converted to 3,
Polyimide powder was synthesized in exactly the same manner except that 3 ', 4,4'-tetraaminodiphenyl ether was used.
The relationship between the molar ratio of 4,4′-bis (3-aminophenoxy) biphenyl and 3,3 ′, 4,4′-tetraaminodiphenyl ether and the melt viscosity of the obtained polyimide at 420 ° C. is shown as the result of Synthesis Example 2. The results are collectively shown in Table 2.

Synthesis Example 21 4,4'-bis (3-aminophenoxy) biphenyl of Synthesis Example 2 3.496 kg (9.5 mol), 3,3'-diaminobenzidine 53.5 g (0.25 mol), 2.04 kg (9.35 mol) of pyromellitic dianhydride and 192.4 g (1.3 mol) of phthalic anhydride were added to 3.68 kg (1 of 4,4′-bis (3-aminophenoxy) biphenyl.
0.0 mol), pyromellitic dianhydride 2.07 kg
(9.50 mol) and phthalic anhydride 148 g (1.0 mol), except that the polyimide powder was synthesized in exactly the same manner. Table 2 shows the logarithmic viscosity and melt viscosity of the obtained polyimide.

Synthesis Example 22 4,4'-bis (3-aminophenoxy) biphenyl of Synthesis Example 2 3.496 kg (9.5 mol), 3,3'-diaminobenzidine 53.5 g (0.25 mol), 2.04 kg (9.35 mol) of pyromellitic dianhydride and 192.4 g (1.3 mol) of phthalic anhydride were added to 3,27 Kg of 4,4′-bis (3-aminophenoxy) biphenyl.
(8.883 mol), 3,3'-diaminobenzidine 5
0.1 g (0.234 mol), pyromellitic dianhydride 2.18 Kg (10. mol), aniline 120.9 g
Polyimide powder was synthesized in exactly the same manner except that the amount was changed to (1.3 mol). Table 2 shows the logarithmic viscosity and melt viscosity of the obtained polyimide.

[0043]

[Table 2] Table 2 ─────────────────────────────────── Synthesis example Number of moles of amino compound used A B B / A η Melt viscosity Diamine Tetraamino (molar ratio) (dl / g) (poise) Compound and / or triamino compound ────────────────────── ────────────── 10 BP / 9.9 TAPB * 10) /0.15 0.015 0.49 5800 11 BP / 9.8 TAPB / 0.3 0.03 0.50 6000 12 BP / 9.5 TAPB / 0.75 0.08 0.51 6300 13 BP / 9.3 TAPB / 1.05 0.11 0.49 7100 14 BP / 9.0 TAPB / 1.5 0.17 0.50 24000 15 BP / 9.9 TABP * 11) /0.15 0.015 0.50 5100 16 BP / 9.9 TAB * 12) /0.15 0.015 0.49 5700 17 BP / 9.9 TAP * 13 ) /0.15 0.015 0.51 6200 2 BP / 9.8 DAB * 14) /0.10 0.01 0.50 9000 18 BP / 9.9 DAB / 0.05 0.005 0.51 5600 19 BP / 9.0 DAB / 0.5 0.056 0.51 5900 20 BP / 9.9 TADE * 15) /0.15 0.015 0.50 5200 21 BP / 10.0 0 0 0.51 8000 22 BP / 9.8 DAB / 0.10 0.01 0.50 9000 ──────────── ─────────────────────── * 10) 1,3,5-Tris (4-aminophenoxy) benzene * 11) 3,3 ', 4- Triaminobenzophenone * 12) 1,2,4-triaminobenzene * 13) 2,4,6-triaminopyrimidine * 14) 3,3'-diaminobenzidine * 15) 3,3 ', 4,4'- Tetraaminodiphenyl ether

Example 1 30 parts by weight of carbon fiber (HTA-C6) manufactured by Toho Rayon was added to 70 parts by weight of the polyimide powder obtained in Synthesis Example 2 and mixed by a drum blender mixer (manufactured by Kawada Seisakusho). Then, after melt-kneading at 400 ° C. with a single-screw extruder having a diameter of 30 mm, the strand was air-cooled and cut to obtain pellets. Using the pellet obtained, an injection pressure of 500 kg / cm ² and a cylinder temperature of 4 were measured by an Arburg injection molding machine.
Injection molding was performed under the conditions of 10 ° C and a mold temperature of 180 ° C to obtain a tensile test piece. JIS K7 using this test piece
According to 118, the number of repeated fatigues was measured by the partial swing method. Table 3 shows the relationship between the load and the number of repeated fatigues.

Examples 2 to 19 Using the polyimide powders obtained in Synthetic Examples 3 to 13 and Synthetic Examples 15 to 20 and Synthetic Example 22, tensile test pieces were prepared in the same manner as in Example 1 to measure the number of repeated fatigues. did. The results are also shown in Table 3.

Comparative Examples 1 and 2 Using the polyimide powders obtained in Synthesis Example 14 and Synthesis Example 21, tensile test pieces were prepared in exactly the same manner as in Example 1 and the number of repeated fatigues was measured. The results are also shown in Table 3.

[0047]

[Table 3] (Table 3) ─────────────────────────────────── Fatigue characteristics of polyimide injection molded products Synthetic example Maximum excitation stress (Kg / mm ² ) Repeated fatigue count (times) ───────────────────────────────── Example 1 2 12 3200.0x10 ⁵ Example 2 3 12 2900.0x10 ⁵ Example 3 4 12 3000.0x10 ⁵ Example 4 5 12 2200.0x10 ⁵ Example 5 6 12 1900.0x10 ⁵ Example 6 7 12 2400.0x10 ⁵ Example 7 8 12 2600.0x10 ⁵ Example 8 9 12 2200.0x10 ⁵ Example 9 10 12 4300.0x10 ⁵ Example 10 11 12 4100.0x10 ⁵ Example 11 12 12 3200. 0x10 ⁵ example 12 13 12 110 .0X10 ⁵ Example 13 15 12 3200.0x10 ⁵ Example 14 16 12 2900.0x10 ⁵ Example 15 17 12 3000.0x10 ⁵ Example 16 18 12 1900.0x10 ⁵ Example 17 19 12 2800.0x10 ⁵ Example 18 20 12 3300.0x10 ⁵ Example 19 22 12 3100.0x10 ⁵ Comparative Example 1 14 12 * A) Comparative Example 2 21 12 1.5x10 ⁵ ───────────────── ────────────────── * A) Injection molding is not possible

Example 20 30 parts by weight of glass fiber (RES-03) made by Nippon Sheet Glass was added to 70 parts by weight of the polyimide powder obtained in Synthesis Example 2 and mixed by a dry blender mixer (manufactured by Kawata Seisakusho). 400 ° C by a single-screw extruder with a diameter of 30 mm
After melt-kneading with, the strand was air-cooled and cut to obtain pellets. Using the pellets thus obtained, injection molding was carried out with an Arburg injection molding machine under the conditions of an injection pressure of 500 kg / cm ² , a cylinder temperature of 410 ° C. and a mold temperature of 180 ° C.
A tensile test piece was obtained. Using this test piece, JIS K7
According to 118, the number of repeated fatigues was measured by the partial swing method. When the maximum excitation stress was 4 kg / mm ² , the number of repeated fatigue was 2800 × 10 ⁵ .

[0049]

EFFECTS OF THE INVENTION According to the method of the present invention, a polyimide resin composition and an injection-molded article having excellent fatigue resistance are provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technology display location // B29K 79:00 (72) Inventor Yoshihiro Sakata 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals

Claims (5)

[Claims] 1. Formula (I) [Chemical Formula 1] [Chemical Formula 1] Means ) With respect to 1 mol of the diamine compound represented by the following formula (II) Means ) Tetraamino compound represented by
Alternatively, the following formula (III) [Chemical Formula 3] Means ), The sum of the triamino compounds represented by
An amine compound of 005 to 0.11 mol and the following formula (I
V) [Chemical 4] [Chemical 4] Is a tetravalent group. ), Which is obtained by reacting a tetracarboxylic acid dianhydride component with a dicarboxylic acid anhydride or a monoamino compound in the presence or absence of the compound, and is capable of being melt-molded with excellent fatigue properties. Polyimide resin, a polyimide resin composition comprising the polyimide resin and carbon fiber, and an injection molded article thereof. 2. A diamine compound represented by the above formula (I) and a tetracarboxylic acid represented by the above formula (II) per 1 mol of the tetracarboxylic dianhydride represented by the above formula (IV). The total sum of amino compounds having two or more amino groups consisting of an amino compound and / or a triamino compound represented by the above formula (III) is 0.8 to 1.20 mol. 1. A melt-moldable polyimide resin having excellent fatigue properties as described in 1. 3. Fatigue according to claim 1, wherein 0.001 to 0.20 mol of dicarboxylic acid anhydride and / or monoamine is used with respect to 1 mol of the total amount of the tetracarboxylic dianhydride. Melt-moldable polyimide resin with excellent properties. 4. The polyimide resin 100 according to claim 1.
A polyimide resin composition containing 5 to 100 parts by weight of a fibrous reinforcing material with respect to parts by weight. 5. An injection-molded article containing the polyimide resin according to claim 1.